Procedure for manufacturing catalyst components for polymerizing olefines

ABSTRACT

The invention concerns a procedure for manufacturing solid catalyst components for catalysts serving polymerization of alpha-olefines, having a solid carrier substance containing an organic or inorganic magnesium compound and treated with a titanium halide and optionally with an electron donor compound. The magnesium compound or the mixture of magnesium compound and electron donor compounds is sprayed in molten state into a chamber or volume which has been cooled to a temperature at which the catalyst component will solidify from the melt in the form of particles with generally spherical shape, without any substantial evaporation of solvents.

BACKGROUND OF THE INVENTION

The present invention relates to a procedure for manufacturing catalystcomponents to be used in polymerizing olefines. In particular theinvention relates to the manufacturing of catalyst and carriercomponents having spherical shape, for olefin-polymerizing catalysts.

The use of Zieglar-Natta catalysts towards polymerizing olefines isknown in the art. Such catalysts typically comprise a magnesium-basedcarrier substance which has been treated with a titanium halogencompound, and often also with an electron donor compound. Numerousmethods have been worked out for manufacturing catalysts of this type,and a very great number of different compounds have been applied inorder to modify said typical catalysts.

It is desirable in view of polymerizing that the catalysts have highestpossible activity and thereby the required catalyst quantity is as smallas possible. It is furthermore possible by the selection of catalyst toinfluence many other polymerization characteristics. Endeavours arefrequently directed towards a result in which the products that areobtained would be in the form of even-sized, preferably sphericalparticles. This is reached, for instance, by the aid of using a catalystcarrier substance which occurs in the form of spherical particles ofuniform quality.

Various methods are known in the art for producing carrier particleswith spherical shape. In the so-called emulsion oil method, a melt ofthe carrier component is emulsified in a suitable oil, to be presenttherein in the form of spherical melt particles. The carrier particlesin the emulsion are then shock-solidified by adding the emulsion into acold hydrocarbon fluid, where the particles solidify. One of thedrawbacks of this procedure is that preparing the carrier substancerequires a component which is not useful in the later steps of catalystmanufacturing and which implies the existence of purifying andrecirculation apparatus to this purpose. Another significant drawback isthat this a charge process, in which the retention time is oftenprolonged, even up to several hours.

Another technique of the prior art for preparing particles of sphericalshape for catalysts is the so-called spray drying method. For instance,in the GB Pat. No. 1,434,543 is disclosed a procedure wherein magnesiumchloride is sprayed in molten state, or in aqueous solution, into hotair or nitrogen with the aid of a nozzle having such size that theparticles which are formed will have the requisite particle size. In theU.S. Pat. No. 4,506,027, an equivalent procedure has been disclosedwherein ethanol and methanol solution of magnesium chloride is sprayedin droplet from into a hot nitrogen flow. The spray drying techniquedisclosed in these patents which have been described is based on theexpedient that from the droplets produced in the nozzle, fluid isevaporated off with the aid of a hot, inert gas and as ultimate resultsolid carrier particles which are generally round in shape are obtained.

The spray drying method has some drawbacks which are partly associatedwiht the quality of the carrier components obtained by the method andpartly also with the process factors themselves. In spray drying, when asolvent is used, a change of the chemicals composition takes place allthe time as solvent, to begin with, evaporates from the solution and,thereafter, from the surfaces of the solid carrier particles. As aconsequence, the composition of the particles that are produced is notfully under control. The continuous evaporation of solvent from theparticles causes growth of the particles' surface area and finally leadsto particles which are porous and non-uniform in quality, containingvarying amounts of solvent. Porosity detracts from the mechanicaldurability of the catalyst components and also impairs the activity ofthe catalyst that is obtained and its morphological properties. Anotherdrawback is associated with the safety considerations of the process.Since the method is based on evaporating solvents, a consequence is thatone has to handle great solvent quantities in gaseous form, and thisinvolves a safety risk. Furthermore, comparatively high temperatureshave to be used in the process, and this is not appropriate for allchemicals which are required.

SUMMARY OF THE INVENTION

With the aid of the invention a procedure is achieved by the aid ofwhich catalyst components can be manufactured in spherical shape withoutincurring the drawbacks connected with the above processes. Inparticular, with the aid of the invention a procedure is achieved inwhich carrier components with spherical shape can be produced which alsocontain other active, or inert, additives or components required in thecatalyst component. Furthermore, it is possible by the procedure of theinvention to manufacture in one single step even fully completedcatalyst components which are then directly usable asolefine-polymerizing catalysts.

These, and other advantages which will become apparent later on, areachieved with the procedure of the invention for manufacturing solidcatalyst compounds for such polymerizing catalysts for alpha-olefinescontaining more than two carbon atoms, or copolymerizing catalysts forone or several alpha-olefines as mentioned and ethylene which comprise asolid carrier substance containing an organic or inorganic magnesiumcompound, treated with a titanium halide and with an electron donorcompound.

The procedure of the invention is characterized in that said magnesiumcompound, or a mixture of said magnesium compound and said electrondonor compound, is sprayed in molten state into a chamber, or volume,which has been cooled to a temperature at which the catalyst componentsolidifies from said melt in the form of particles with generallyspherical shape, without any substantial evaporation of components,whereafter said titanium halide treatment is carried out.

By the procedure of the invention several advantages are gained,compared with the spray drying technique. In the procedure of theinvention the composition of the carrier solution is constant all thetime and no solvent evaporation takes place, as is the case in the spraydrying process. The particles that are produced are therefore uniform inquality and their structure is not porous as is that of particlesproduced by the spray drying method. The composition of the particlescan be adjusted to be as desired, and it is thus understood that thecomposition does not change during the manufacturing process. As aconsequence, the particles are also more durable mechanically. Secondly,according to the invention the formation of particles takes place atcomparatively low temperatures, at which the chemicals and solvents thatare used neither evaporate nor decompose. The process is also safebecause it is not necessary to evaporate large quantities of solvent.

A significant additional advantage of the procedure of the invention isthat with its aid it is possible, in one apparatus and in one step, toproduce either exclusively spherical carrier particles or carrierparticles which contain other active, or inert, substances needed in thecatalyst, or even fully completed active catalyst components which aredirectly applicable in polymerizing olefines. This is not possible inthe spray drying method of prior art.

The procedure of the invention is suitable for manufacturing carriercomponents of both inorganic and organic magnesium compounds,advantageously of halogenated magnesium compounds.

Examples of inorganic magnesium compounds are, for instance, magnesiumchloride and magnesium compounds obtained from inorganic magnesiumcompounds by the aid of chlorinating agents, such as chlorine andhydrochloric acid. A recommendable inorganic magnesium compound ismagnesium chloride. Examples of organic magnesium compounds are thosecompounds which are obtained when organic magnesium compounds, such asmagnesium alkyl compounds, react with chlorinating compounds. Examplesof said magnesium alkyl compounds are: diethylmagnesium,ethylbutylmagnesium, ethylhexylmagnesium, ethyloctylmagnesium,dibutylmagnesium, butylhexylmagnesium, butyloctylmagnesium,dicyclohexylmagnesium. A recommendable magnesium alkyl compound isbutyloctylmagnesium.

By the procedure of the invention carrier and catalyst components can bemanufactured which contain, in addition to the above-mentioned magnesiumcompounds, electron donor compounds such as are normally used in thiskind of catalysts as well as other auxiliary substances which may berequired. For auxiliary substances, alcohols are advantageously used,for instance methanol or ethanol. It is only a prereqisite for using adonor that the donor when mixed with a solid magnesium compound onheating forms a melt which can be sprayed with the aid of a nozzle. Theelectron donor may thus be selected from the group comprising aliphaticor aromatic carboxylic acids, aliphatic or aromatic alkylesters ofcarboxylic acids, ethers, aliphatic or aromatic ketones, aliphatic andaromatic aldehydes, aliphatic and aromatic alcohols, aliphatic andaromatic halides, e.g. acid halides, aliphatic and aromatic nitriles,aliphatic and aromatic amines aliphatic, and aromatic phosphines andphosphines and aromatic and aliphatic silicon ethers. An advantageouscombination of magnesium compound and electron donor and/or auxiliarysubstance can be described by the following formula: MgCl₂.LOH.ySKY,wherein x=1 to 6, y=0 to 1.0 and LOH and SKY have been selected from theabove-mentioned class of electron donors. A highly recommendable andfrequently used electron donor is diisobutylphthalate, and arecommendable alcohol is ethanol. LOH may be a lower alkyl alcoholcontaining between 1 to 10 carbon atoms.

The mixture to be sprayed is prepared simply by melting the selectedcatalyst component or component mixture. The melt is conducted into thespaying chamber with the aid of a pump or advantageously of apressurized, inert fluid, for instance nitrogen.

In the procedure of the invention the melt, or solution, of the carriercompound is sprayed into a cooled chamber at a temperature which atleast equals the melting point of said carrier compound which is used,advantageously one approximately equal to the melting point. Sphericalparticles are manufactured by conducting the melt with the aid ofpressure to a nozzle located in the varying chamber, with nozzledispersing it into fine droplets. It is possible with the choice ofnozzle size to influence the size and size distribution of the carrierparticles which are produced in the process. At the same time, coldinert gas, for instance nitrogen or air, is conducted through the bottomof the chamber upward from below, which rapidly cools the particlescoming from the nozzle. The cooling may be enhanced by spraying at thesame time into the chamber a cold, inert hydrocarbon or another liquidfluid. It is not necessary to spray the cooling gas or cooling fluidinto the chamber in countercurrent to the sprayed melt. It is alsopossible to spray cooling fluid with the current of the melt spray if inthis way fast enough solidifying to solid particles is achievable. Whatis essential in the cooling event is that the cooling is so fast thatthe melt solidifies to solid state before it hits the walls of theapparatus and that no significant evaporation of the componentscontained in the carrier substance has time to take place. The catalystparticles fall down on the bottom of the spraying chamber or to thelayer of liquid accumulating there, wherefrom they can be removedthrough the lower part of the spraying chamber. The inert gases escapingfrom the upper part may be carried through a cyclone in order toseparate any small carrier particles which may have been entrained.

As has been said in the foregoing, it is possible in the procedure ofthe invention to manufacture, as may be required, either mere carriersubstance particles or carrier particles containing, in addition, otherinert or active auxiliary substances. It is thus for instance possibleto manufacture adducts formed by magnesium chloride and an alcohol,which are easy to activate to become a completed catalyst. Frommagnesium chloride and ethanol, for instance, a carrier component can bemanufactured in the procedure of the invention in that a mixture ofmagnesium and ethanol is heated in an autoclave, in a nitrogenatmosphere, at least to its melting point or preferably slightly higher.Th melting point is essentially dependent on the ethanol quantity added.Compressed nitrogen is used to supply the molten mixture into thecooling chamber with the aid of a nozzle, which disperses the melt intosmall droplets. At the same time cold inert cooling gas, such asnitrogen or air (e.g. -20° C.), is supplied into the chamber and, ifrequired, also an inert cooling liquid, e.g. heptane. Solid carrierparticles will then be formed which have a diameter on the order of0-100 μm. The carrier particles accumulating on the bottom of thechamber are removed for further treatment, which may for instance betreatment with an electron donor, or an activation treatment. Thecarrier particles are at this time already at a suitable temperature forthe next treatment.

The procedure of the invention further enables such carrier componentsto be manufactured in the same apparatus which contain theabovementioned electron donor compounds. In that case, the exemplarycase described above may be modified so that the substance mixture whichis sprayed into the chamber contains, in addition to the magnesiumcomponent and the ethanol component, an electron donor component. Thecarrier particles which solidify in the chamber may then be carrieddirectly to the next manufacturing step, that is, to activation, forinstance to titanizing, in which the treatment is carried out withtitanium tetrachloride. In the same way other active components may beadded to the carrier component.

The procedure of the invention may further be applied in manufacturingcompleted catalysts treated with titanium tetrachloride. The ways abovedescribed may then be applied so that for cooling fluid is used, insteadof an inert fluid, cold titanium tetrachloride, which may be sprayedagainst the melt spray coming from the nozzle. In that case simultaneoussolidification of the catalyst component to solid particles andactivation of the catalyst component to a completed, active catalystcomponent will take place, the latter being directly usable forpolymerizing, or subjectable to various additive treatments if required.

In the procedure that has been described, the cooling during the firstactivation step renders possible high activity of the catalyst becausethe efficient cooling prevents unfavourable temperature increase duringthe titanizing in the first step.

BRIEF DESCRIPTION OF THE DRAWING

The invention is further illustrated by referring to the appendedFIGURE, which presents an apparatus appropriate for applying theprocedure of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The apparatus 10 of the invention comprises a mixing tank 11 for mixingand melting the catalyst components and into which the catalystcomponents which are used, such as carrier component, alcohol orelectron donors, can be introduced through the connector 12. Into themixing tank 11 may also be conducted inert, pressurized nitrogen gasthrough the pipe 13, and the mixing tank 11 has in addition beenprovided with heating means 14 for melting the catalyst componentmixture. The mixture melted in the mixing tank 11 is conducted with theaid of nitrogen pressure by the heat-escorted pipe 15 to the sprayingchamber 16, to the nozzle 17, where it is dispersed into small droplets.Into the spraying chamber 16 is also conducted cold inert cooling gas bythe nozzles 18 and cold liquid cooling fluid with the aid of the pipe 19and nozzles 20. From the upper part of the chamber 16, the gases escapethrough the pipe 21 to a separator 22, where any solid catalystcomponents that may have been entrained can be removed. The solidifiedcatalyst particles are removed from the lower part of the chamber 16 bythe pipe 23 to a product container 24, in which for instance the nexttreatment step may be carried out, which may for instance be treatmentwith an electron donor compound or activation, or additional activation.

EXAMPLE 1

A nitrogenated autoclave of capacity 110 liters was charged with 35 kgof dry MgCl₂, 65liters of dry EtOH and 10 liters of diisobutylphthalate.This reaction mix was melted at +110° C., with mixing at the ultimatestage. After mixing for 2 hrs. the clear, homogenized mixture wassupplied at a rate of 10 kg/h into a cooled spray chamber, into whichnitrogen at -20° C. was conducted for cooling fluid. The nozzle type wasa 9-mm gas/liquid fluidizing nozzle with melt feeding aperture 1.0 mm indiameter and spraying angle 60°. Dried nitrogen at +130° C. served asspraying gas, its feed rate being 1 kg/h. The product was free-flowingand spherical in shape, and it emerged at temperature about 0° C.

The analytic result was Mg 9.2% by wt. and Cl 26.3% by wt., according towhich the chemical composition of the product was the same as that ofthe starting material melt: MgCl₂ . 3 EtOH . 0.1 DIBP.

The particle size distribution was in the range 10-300 microns. Thefraction <74 microns was separated from the product by screening, foractivation of the catalyst carrier. Preparation of carrier and catalystwas performed in a nitrogen atmosphere with H₂ O<5 ppm and O₂ <5 ppm.Activation took place as follows, using TiCl₄ /EtOH mole ratio: 8.7:27.2 g of the above, screened product were added at 0° C. into 300 ml ofTiCl₄. The carrier was allowed to react at this temperature for 1 hr,with mixing. The temperature was then slowly raised to +120° C., and itwas kept at this height for 2 hrs. The treatment was repeated with 300ml of TiCl₄ at +120° C. for 2 hrs. The product was further washed with300 ml of heptane at +70° C. The washing was repeated five times, andthe product thus obtained was dried in vacuum at room temperature. Thedry catalyst had violet colour.

The analytic results of the catalyst were: Ti 2.4% by wt.: Mg 16.9% bywt., and Cl 50.5% by wt.

Polymerizing was carried out in a 2-liter autoclave, using 1.2 liters ofheptane for fluid, as follows:

    ______________________________________                                        P(C.sub.3 H.sub.6) = 9.7 bar                                                                   Al/Ti = 200                                                  P(H.sub.2) = 0.3 bar                                                                           Al/Donor = 20                                                T = +70° C.                                                                             Catalyst quantity = 32.0 mg                                  t = 3 h                                                                       ______________________________________                                    

For cocatalyst triethylaluminium was used and for electron donor,diphenyldimethoxysilane.

The activity of the catalyst was 334 kg polypropylene per g Ti.

The evaporation residue from the polymerizing fluid was 0.8% by wt.,referred to the total polypropylene quantity obtained. The polypropylenehad isotacticity 99.2%, isotacticity index 98.6% and specific density0.46 g/cm³. The melt index of the polymer was 4.4 g/10 min. The polymerthat was obtained was round in shape and free-flowing. The polymer hadthe following particle distribution:

    ______________________________________                                        Particle size, mm                                                                           % by weight of the product                                      ______________________________________                                        >2.0          0.1                                                             2.0-1.0       79.1                                                            1.0-0.5       16.7                                                             0.5-0.18     2.4                                                             0.18-0.10     0.8                                                              0.10-0.056   0.6                                                             <0.056        0.3                                                             ______________________________________                                    

Preparation of catalyst carrier, activation and polymerization wererepeated, in the way described above. The analytic results of thecatalyst were: Ti 2.0% by wt., Mg 16.7% by wt., and Cl 51.3% of wt. Theresults of polymerizing were as follows. The activity of the catalystwas 345 kg polypropylene per g Ti. The evaporation residue from thepolymerizing fluid was 2.2% by wt. of the total quantity of polymerobtained. The polymer had isotacticity 99.2%, isotacticity index 97.0%and specific gravity 0.47 g/cm³. The melt index of the polymer was 7.1g/10 min. The polymer that was obtained was round in shape andfree-flowing. The particle size distribution of the polymer was:

    ______________________________________                                        particle size, mm                                                                           % by weight of the product                                      ______________________________________                                        >2.0          0.2                                                             2.0-1.0       70.5                                                            1.0-0.5       20.9                                                             0.5-0.18     6.1                                                             0.18-0.10     1.3                                                              0.10-0.056   0.7                                                             <0.056        0.3                                                             ______________________________________                                    

The quality characteristics of the catalyst activated by the catalystcarrier manufacturing procedure of the invention are eminentlyreproducible, which is a decisive factor in process catalystmanufacturing.

EXAMPLE 2

An MgCl₂ /ethanol/DIBP mixture was melted at +120° C. andspraycrystallized as in Example 1, with the exception that the DIBP/Mgratio was 0.05.

    ______________________________________                                        Particle size, microns                                                                       % by weight of total weight                                    ______________________________________                                        >105           30.2                                                           105-74         33.7                                                           <74            36.1                                                           ______________________________________                                    

The particle size distribution of the solid product was: The analyticresult was: Mg 9.6% by wt., Cl 27.8% by wt., corresponding to thecomposition of the input melt, MgCl₂ . 3 EtOH . 0.05 DIBP.

The catalyst was prepared as in Example 1.

The analytic results of the catalyst were: Ti 3.5% by wt., Mg 13.0% bywt., and Cl 50.6% by wt.

Propylene was polymerized with the catalyst as in Example 1.

The performance of the catalyst and characteristics of the polymer were:

    ______________________________________                                        Activity           279 kg PP per g Ti                                         Isotacticity       94.5%                                                      Evaporation residue                                                                              7.7%                                                       Isotacticity index 87.2%                                                      Melt index         12.1 g/10 min.                                             Specific density   0.45 g/cm.sup.3                                            ______________________________________                                    

The morphology of the polypropylene was spherical, but it was slightlysticky owing to low isotacticity index.

The particle size distribution of the polymer was:

    ______________________________________                                        Particle size, mm                                                                           % by weight of the product                                      ______________________________________                                        >2.0          0.1                                                             2.0-1.0       65.3                                                            1.0-0.5       29.0                                                             0.5-0.18     4.7                                                             0.18-0.10     0.5                                                              0.10-0.056   0.4                                                             <0.056        --                                                              ______________________________________                                    

EXAMPLE 3

A nitrogenated autoclave of capacity 110 liters was charged with 35 kgof dry MgCl₂ and 80 liters of dry EtOH. This reaction mix was melted at140° C., with mixing at the ultimate stage. After mixing for 8 hrs, theclear, homogenized mixture was supplied at a rate of 10 kg/h into acooled spray chamber, which was cooled with nitrogen at -20° C. Thenozzle type was a 9-mm gas/liquid fluidizing nozzle with melt feedingaperture 1.0 mm in diameter and spraying angle 60°. Nitrogen at 140° C.served as spraying gas, its feed rate being 1 kg/h.

The product was free-flowing and spherical in shape. The product had thesame chemical composition as the starting material melt (MgCl₂ . 3.7EtOH). The particle distribution was in the range 10-300 microns. Thefraction <74 microns was separated from the product by screening, foractivation.

Activation took place as follows. 6.9 g of the above, screened productwere added at 0° C. into 200 ml of TiCl₄. (TiCl₄ /EtOH moleproportion=20). The carrier was allowed to react at this temperature for1 hr, with mixing, whereafter 1.2 ml of diisobutylphtalate (DIBP/Mg moleproportion=0.2) were added and the temperature was slowly raised to+110° C., for 1 hr. The treatment was repeated with 200 ml of TiCl₄ at+110° C. for 1 hr. The product was further washed with 300 ml of heptaneat +70° C. The washing was repeated five times, and the product thusobtained was dried in vacuum at room temperature. The analytic resultsof the catalyst were:

Ti 1.5% by wt.; Mg 15.6% by wt., and Cl 47.0% by wt.

Polymerizing was performed as in Example 1. The activity of the catalystwas 380 kg polypropylene per g Ti. The evaporation residue from thepolymerizing fluid was 0.5% by wt: of the total quantity of polymerobtained. The isotacticity of the polypropylene was 98.0%, isotacticityindex 97.5% and specific gravity 0.40 g/cm³. The particle sizedistribution of the polymer was:

    ______________________________________                                        Particle size, mm                                                                           % by weight of the product                                      ______________________________________                                        >2.0          0.10                                                            2.0-1.0       43.4                                                            1.0-0.5       37.9                                                             0.5-0.18     15.1                                                            0.18-0.10     2.2                                                              0.10-0.056   1.0                                                             <0.056        0.3                                                             ______________________________________                                    

EXAMPLE 4

An MgCl₂ melt was spray-crystallized as in Example 3, except that theEtOH/MgCl₂ proportion was 2.9.

The solid product had the following particle size distribution:

    ______________________________________                                        Particle size, microns                                                                         % of total weight                                            ______________________________________                                        >105             42.2                                                         105-74           27.6                                                         <74              30.2                                                         ______________________________________                                    

The analytic result was: Mg 11.1% by wt., Cl 30.2% by wt. On the basisof the analytic data, the gross formula of the complex corresponds toMgCl₂ . 2.9 EtOH.

Morphologically, the product was free-flowing, spherical powder. 0.105moles of MgCl₂ . 2.9 EtOH with size <74 microns were activated as inExample 3, with the exception that the TiCl₂ /EtOH mole proportion was8.7 in the first and second titanizing. The DIBP/Mg molar proportionemployed was 0.2. The analytic results of the catalyst were: Ti 4.6% bywt., Mg 13.1% by wt., and Cl 52.3% by wt.

The catalyst was used to polymerize propylene as in Example 1.

The performance of the catalyst and the characteristics of the polymerwere as follows:

    ______________________________________                                        Activity           215 kg PP per g Ti                                         Isotacticity       99.7%                                                      Evaporation residue                                                                              1.5%                                                       Isotacticity index 98.2%                                                      Melt index         11.8 g/10 min.                                             Specific density   0.42 g/cm.sup.3                                            ______________________________________                                    

The polypropylene had spherical morphology.

The particle size distribution of the polymer was:

    ______________________________________                                        Particle size, mm                                                                           % by weight of the product                                      ______________________________________                                        >2.0          0.1                                                             2.0-1.0       60.9                                                            1.0-0.5       35.4                                                             0.5-0.18     4.0                                                             0.18-0.10     0.4                                                              0.10-0.056   0.2                                                             <0.056        --                                                              ______________________________________                                    

COMPARISON EXAMPLE 1

A catalyst was prepared otherwise as in Example 4, but MgCl₂ . 3 EtOHwas used for starting material and preparation took place withoutdiisobutylphthalate. The catalyst had yellowish-brown colour. Theanalytic data of the catalyst were: Ti 9.2% by wt., Mg 12.8% by wt., andCl 59.0% by wt.

Polymerizing was performed as in Example 1. The activity of the catalystwas 75 kg PP per g Ti. The evaporation residue from the polymerizingfluid was 17.4% by wt. of the total polymer quantity obtained. Thepolypropylene had isotacticity 79.4% and isotacticity index 65.6%. Itsspecific density could not be determined because the solid polymer wasagglomerated and it was not free-flowing.

The result of polymerization clearly reveals that if no electron donorcompound is used in conjunction with catalyst preparation, the activityof the catalyst and the isotactic properties and morphologicalcharacteristics of the polypropylene are so poor that the catalyst failsto meet the quality requirements commonly imposed on stereo-specificalpha-olefine polymerizing catalysts. A catalyst of this type also isnot appropriate for use in polymerizing processes (e.g. polypropylene,polybutylene, poly-4-methyl-pentylene, etc.).

COMPARISON EXAMPLE 2

The component to be sprayed was prepared as in Example 3, except thatthe EtOH/MgCl₂ molar proportion was 8, and TiCl₄ was added to themixture applying MgCl₂ /TiCl₂ molar proportion 1. The product thusobtained was melted at +90° C. and spray-crystallized.

The product which was obtained had the composition: MgCl₂ TiCl₂ (OEt)₂ .6.0 EtOH.

40 g of the above product were admixed to 300 ml of heptane, and to thesuspension that was obtained were added 550 ml of 10% by vol. of Al₂ Et₃Cl₃ /heptane solution at room temperature (0.22 mol of Al₂ Et₃ Cl₃). Thesuspension was mixed at room temperature for 1/2 hr, and thereafter for1 hr at +85° C. The product thus obtained was washed five times with 300ml of heptane at +70° C. adn dried with vacuum. The catalyst had lightbrown colour.

The analytic results of the catalyst were: Ti 3.2% by wt., Mg 15.0% bywt., Cl 59.9 by wt.

Polymerizing was performed as in Example 1. The activity of the catalystwas 70 kg PP per g Ti. The evaporation residue from the polymerizingfluid was 15.1% of the total polymer quantity obtained. Thepolypropylene presented isotacticity 95.5% and isotacticity index 81.0%.Specific density was 0.36 g/cm³.

The result of polymerization clearly reveals that the activity of thecatalyst and the isotacticity index and specific density of thepolypropylene are so poor that the catalyst fails to meet the qualityrequirements imposed on stereo-specific alpha-olefine polymerizingcatalysts. A catalyst of this type is therefore not appropriate for usein polymerizing processes (e.g. polypropylene, polybutylene,poly-4-methyl-1-pentylene, etc.).

We claim:
 1. A procedure for manufacturing solid catalyst components forcatalysts serving polymerization of alpha-olefines containing more thantwo carbon atoms, or copolymerization of one or several of thesealpha-olefines and ethylene, of the kind which comprises a solid carriersubstance containing an organic or inorganic magnesium compound andtreated with a titanium halide and with an electron donor compound,whereinsaid magnesium compound or a mixture of said magnesium compoundand said electron donor compound is sprayed in molten state into achamber or volume which has been cooled to a temperature at which thecatalyst component will solidify from the melt in the form of particleswith generally spherical shape, and without an substantial evaporationof solvent, whereafter said titanium halide treatment is carried out ,wherein said magnesium compound or said mixture is of the form MgCl₂(xLOH)ySKY, where x=1 to 6, y=0 to 1.0, and LOH and SKY are eachselected from the group consisting essentially of aliphatic or aromaticcarboxylic acids, aliphatic or aromatic alkyl esters of carboxylicacids, ethers, aliphatic or aromatic ketones, aliphatic or aromaticaldehydes, aliphatic or aromatic alcohols, aliphatic or aromatichalides, aliphatic or aromatic nitriles, aliphatic or aromatic amines,aliphatic or aromatic phosphines or phosphites, and aliphatic oraromatic silicon ethers.
 2. Procedure according to claim 1, wherein SKYhas been selected from the group consisting essentially of aromaticmono-, di- or poly-carboxylic acid esters, anhydrides and acid halides.3. Procedure according to claim 1, wherein the Mg compound is ahalogenated organic Mg compound.
 4. Procedure according to claim 1,wherein the titanium compound is titanium tetrachloride.
 5. Procedureaccording to claim 1, wherein the chamber is cooled with the aid of acold, inert gas which is conducted in countercurrent or with the currentwith reference to the melt that is being sprayed.
 6. Procedure accordingto claim 1, wherein the chamber is cooled with the aid of an inert, coldliquid fluid.
 7. Procedure according to claim 1, wherein the cooling isaccomplished with the aid of titanium tetrachloride.
 8. The procedure ofclaim 1, wherein LOH is a lower alkyl alcohol containing 1 to 10 carbonatoms.
 9. The procedure of claim 5, additionally comprisingspraying coldinert hydrocarbon into said chamber to enhance cooling.
 10. Theprocedure of claim 1, additionally comprisingspraying cooling gas orfluid into said chamber co-currently to the spraying of the melt. 11.The procedure of claim 1, wherein the particles formed principally havediameters up to about 100 microns.
 12. The procedure of claim 1, whereinsaid magnesium compound/electron donor mixture is MgCl₂ (3 EtOH)0.1diisobutylphthlate.
 13. The procedure of claim 1, wherein said magnesiumcompound/electron donor mixture is MgCl₂ (3 EtOH) 0.05diisobutylphthlate.
 14. The procedure of claim 1, wherein said magnesiumcompound is MgCl₂ (3.7 EtOH).
 15. The procedure of claim 1, wherein saidmagnesium compound is MgCl₂ (2.9 EtOH).
 16. The method of claim 1,wherein y=0 and comprising the additional step ofreacting said carriersubstance with diisobutylphthlate after said formation of saidparticles.
 17. The method of claim 14, comprising the additional stepofreacting the particles of said Mg compound with 0.2diisobutylphthlate.
 18. The method of claim 15, comprising theadditional step ofreacting the particles of said Mg compound with 0.2diisobutylphthlate.